Topical anhydrous delivery system for antioxidants

ABSTRACT

This invention relates to an anhydrous composition comprising an antioxidant comprising over 40% by weight of hydrolysable tannins having molecular-weight of less than 1,000 and a substantially anhydrous or non-aqueous liquid vehicle functioning to disperse the antioxidant. The composition is suitable as cosmetic composition and/or therapeutic and/or prophylactic composition and/or anhydrous delivery system of cosmetic and/or pharmaceutical ingredients. The invention further relates to processes for producing such compositions.

FIELD OF INVENTION

This invention relates to novel compositions including but not limitedto cosmetic compositions and/or therapeutic and/or prophylactic novelanhydrous delivery systems of cosmetic and/or pharmaceuticalingredients, and especially those including low molecular-weighthydrolysable tannins (<1,000) found in extracts of Phyllanthus emblica(hereinafter PE extracts), and processes for producing suchcompositions.

As described in U.S. Pat. Nos. 6,124,268, 6,290,996 and 6,362,167incorporated by reference herein, PE extracts provide significant skincare benefits, including, for example, skin-lightening or whiteningeffects and/or anti-oxidant effects and/or skin appearance regulatingeffects. The present invention is applicable to all types of extracts ofPhyllanthus emblica. For example, in French patent 2730408 publishedAug. 14, 1996, compositions are disclosed which are prepared by merelypressing the fruit or obtaining a dilute-alcoholic extract. Both theextracts obtained by pressing and the extracts obtained by alcoholicmaceration may then be concentrated at a moderate temperature underreduced pressure, preferably less than 50° C., then optionally broughtto the dry state by freeze-drying or any other method under reducedpressure and at a temperature that is lower than 50° C. so as to avoiddegrading the active ingredients of the fruit. In greater detail,examples 3, 6 and 8 of the French patent 2730408 illustrate themanufacture and uses of extracts based on Phyllantus emblica.

In this French patent, however, there is no indication of thecomposition of the extracts. Conversely, in U.S. Pat. No. 6,124,268,Ghosal, issued Sep. 26, 2000 entitled “Natural Oxidant Compositions,Method For Obtaining Same And Cosmetic, Pharmaceutical and NutritionalFormulations Thereof” there is set forth the chemical composition ofextracts of Emblica officinalis obtained by extracting the fresh fruitat elevated temperatures, e.g. 70° C., using a very dilute aqueous oralcoholic-water salt solution, e.g. 0.1 to 5%. By this extractionprocess, in the presence of sodium chloride, for example, hydrolysis ofthe glycocidic enzymes in the plant is prevented and the product isprotected from microbial infestation.

In the Ghosal patent, the antioxidant blend of the constituents isdescribed under the name of “CAPROS”, with claim 8, for example, of thepatent setting forth the composition as follows:

An antioxidant blend consisting essentially of, by weight, (1) and (2)about 35-55% of the gallic/ellagic acid derivatives of2-keto-glucono-δ-lactone; (3) about 4-15% of 2,3-di-O-galloyl-4,6-(S)-hexahydroxydiphenoylgluconic acid; (4) about 10-20% of2,3,4,6-bis-(S)-hexahydroxydiphenoyl-D-glucose; (5) about 5-15% of3′,4′,5,7-tetrahydroxyflavone-3-O-rhamnoglucoside; and (6) about 10-30%of tannoids of gallic/ellagic acid.

The common names of the enumerated compounds are (1) and (2) EmblicaninA and Emblicanin B, (3) Punigluconin, (4) Pedunculagin and (5) Rutin.

A preferred antioxidant composition used in the present inventioncomprises a modification of the CAPROS composition, comprising astandardized extract of low molecular weight (<1000) hydrolyzabletannins, over 40%, preferably 50-80% w/w of Emblicanin A, Emblicanin B,Pedunculagin, and Punigluconin with low levels (<1%, w/w) of totalflavonoids whereby the resultant products of the invention can be madeinto elegant white to off-white formulations. Such a composition isdiscussed with greater specificity in pages 28-30 of the August 2001issue of Soap, Perfumery and Cosmetics, the article having the titleIngredients/Emblica, Bearing Fruit, by Ratan K. Chaudhuri. In thearticle that there is no mention, however, of any flavonoids much lessthe maximum acceptable amounts in the composition.

According to the preferred antioxidant composition, the total flavonoidsare maintained at a level which does not impair the desired color, e.g.generally, by weight, less than about 1.0%, preferably less than about0.8%, and even more preferably less than about 0.6%. Also, the desiredconcentrations of the Rutin species of flavonoids(3′,4′,5′,7-tetrahydroxyflavone-3-O-rhamnoglucoside) in the standardizedextract are less than 1.0%, less than 0.01%, less than 0.001% and lessthan 0.0001%, with a value of 0.01 to 0.001% being particularlypreferred. The most preferred concentrations of the components are on apercent by weight basis of the total dried extract: Most PreferredConcentrations % by weight Emblicanin A 20-35 Emblicanin B 10-20Pedunculagin 15-30 Punigluconin  3-12 Total Flavonoids <1

The standardized composition may exhibit average percentage deviationsfrom these preferred values of: Most Preferred Preferred DeviationDeviation Emblicanin A ±10% ±5% Emblicanin B ±10% ±5% Pedunculagin ±10%±5% Punigluconin ±10% ±5% Total Flavonoids ±10% ±5%

The antioxidant composition can be obtained by removal of the totalflavonoids by reversed-phase column chromatography or HPLC using asolvent system of acetonitrile, water/phosphoric acid (20/80/1) or othersolvent combinations as they elute faster than the low molecular-weighttannins. Also, by selection of geographical location, the Phyllanthusemblica fruit extract may provide a substantially lower level of thetotal flavonoids (<1.0%). It has been obser/ed that medium-sized fruitscollected from some parts of eastern India, during October-November,after water extraction and drying, yielded the preferred antioxidantcomposition as a powder with the desired low content of totalflavonoids. Accordingly, by analyzing the total flavonoids content ofextracts and selecting such extracts that contain the desired lowcontent of total flavonoids, it is possible to prepare a standardizedextract.

In the context of the present invention “flavonoids” include a family ofcompounds which exhibit a peak at 350 nm when analyzed by a UVspectrometer. Examples of flavonoids include but are not limited toflavonols and flavones, a species thereof being Rutin as discussedabove.

In a preferred embodiment of this invention a substantiallywater-soluble (over 95% by weight) extract of Phyllanthus Emblicacomprising less than 5% by weight of polymeric tannins, withsubstantially no black specks and at high levels, e.g. over 75% byweight of bio-active, low molecular-weight hydrolysable tannins havingmolecular weights below 1,000 is used. This extract can be obtained byan process which removes ologomeric and polymeric tannins. A suitableprocess comprises the following steps: 1) providing an extract ofPhyllanthus Emblica either resulting from the original extract from theplant, or from a suspension of a powdered composition obtained after theextract is processed, e.g. after a drying step; 2) If necessary,physically separating the black specks and/or precursors thereof and/orpolymeric tannins from the water-soluble components, for example byfiltration with the use of a filter aid; 3) If desired, concentratingthe resultant aqueous solution of the enriched composition of Emblicaofficinalis, for example to a dry powder.

Aqueous formulations of PE extracts are described in theabove-identified patents and applications, these formulations beinggenerally made by introducing a minor amount of powdered PE extractsinto an aqueous solution along with known excipients. Whereas theseformulations are commercially acceptable, a discoloration of suchsolutions has been observed after prolonged storage. The cause of suchdiscoloration is believed to be due to the fact that the PE extractscontain polyphenolic compounds which are susceptible to aerial oxidationon the one hand and hydrolysis on the other hand; however, Applicants donot wish to be bound by this explanation of the mechanism ofdiscoloration.

One aspect of the present invention therefore is to provide a deliverysystem which will inhibit or prevent discoloration, presumably byinhibiting or preventing such aerial oxidation and/or hydrolysis ofactive ingredients, PE extracts in particular. Other aspects of theinvention are to provide a process for producing a final substantiallyanhydrous formulation and the resultant product. Still another aspect isa formulation that provides improved adhesion and skin-feel properties.

Upon further study of this application, other objectives and advantagesof the invention will become apparent.

In order to attain certain objectives of the invention, formulations areprovided which are not based on water, but instead are based on asubstantially anhydrous or non-aqueous vehicle so that the finalformulation contains preferably less than 1% by weight of water. Asidefrom being non-aqueous, the vehicle must be capable of dispersing the PEextracts with adjuvants if necessary. It is also preferred that thenon-aqueous vehicle have an emollient function as well. Classes ofvehicles to be used in the present invention include but are not limitedto silicone fluids, organic esters and glycols.

Examples of silicone vehicles include but are not limited tocyclomethicone, both the tetramer and the pentamer,hexamethyldisiloxane, phenyltrimethicone cross linked polymers ofdimethicone and cyclomethicone (hereinafter “crosspolymer”)methylvinylsiloxanes, methylvinylsiloxane-dimethylsiloxane copolymers,dimethylvinylsiloxy-terminated dimethylpolysiloxanes,dimethylvinylsiloxy-terminated dimethylsiloxane-methylphenylsiloxanecopolymers, dimethylvinylsiloxy-terminateddimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymers,trimethylsiloxy-terminated dimethylsiloxane-methylvinylsiloxanecopolymers, trimethylsiloxy-terminateddimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymers,dimethylvinylsiloxy-terminatedmethyl(3,3,3-trifluoropropyl)polysiloxanes, anddimethylvinylsiloxy-terminateddimethylsiloxane-methyl(3,3-trifluoropropyl)siloxane copolymers, as wellas functional derivatives thereof.

There are, moreover, innumerable polyorganosiloxane oils that aredescribed in the commercial and patent literature, and it is expectedthat still other silicone oils will be developed in the future; so it iscontemplated that all silicone oils will be useful in the presentinvention. For a further description of possible silicone oils that canbe used as vehicles, see the discussion of the use of silicones todisperse particulate vitamin C for use as a topical composition in U.S.Pat. No. 6,146,664, to Siddiqui issued Nov. 14, 2000, especially column8, incorporated by reference herein. Also U.S. Pat. No. 6,475,500 toVatter et al. is of interest since it describes different anhydrous skintreatments including a cross linked siloxane elastomer gel of a specificyield point and volatile siloxane inclusions of the elastomers.

As for the anhydrous organic esters that can be used as vehicles in thepresent invention, preferred are those which also have emollientproperties. Examples of such esters include but are not limited tocetearyl octanoate, caprylic/capric triglyceride, octylhydroxysterate,PPG-2 myristyl ether propionate, tentaerythrityl tetracaprylate/caprate,tentaerythrityl tetraisosterate, natural and synthetic jojoba oils,cetyl acetate, and acetylated lanolin alcohol.

Examples of glycols, include but are not limited to mono- orpoly-alkylene glycols are contemplated, a non-limiting example beingpropylene glycol.

Whereas it is preferred that the vehicle has emollient properties, it isnot necessary to use a vehicle that is also an emollient since it ispossible to add emollients to the mixture of the vehicle and EPextracts.

In the substantially anhydrous formulation, the content of the vehicleis sufficient, generally, about 20-80%, preferably 20-60% by weight ofthe completed formulation to achieve the desired dispersibility of thePE extracts. The content of PE extracts in the formulation is generallyabout from 0.05 to 10%, preferably 0.1-3% by weight, with the preferredminimum weight ratio of the content of the vehicle to the content of thePE extracts being about 20:3.

Another aspect of this invention concerns the preferred addition of atleast one structural and/or gelling agent. Such structural/gellingagents can be combined with the EP extracts to form a mixture comprisingthe PE extract with the structural agent, and/or the gelling agent.Likewise, the structural/gelling agent can be combined with thesubstantially anhydrous vehicle in order to form corresponding mixtureswhich thereafter can be combined with the PE extracts.

The structural agent which provides firmness, structure, consistency andthermal stability to the product can be selected from subgeneric classesof materials which include but are not limited to natural, modified orunmodified waxes, mineral waxes, high melting point fatty alcohols,glycerol or glycol esters, polyethylene and polyethylene glycolpolymers.

Examples of the natural modified or unmodified waxes include but are notlimited to beeswax, candelilla wax, carnauba wax, and hydrogenatedcastor wax.

Examples of mineral waxes include but are not limited to ozokerite andceresin.

Examples of high melting fatty alcohols include but are not limited tocetyl alcohol and stearyl alcohol.

Examples of glycerol or glycol esters include but are not limited toCroda Syncrowaxes, i.e. 18-36 glycol esters.

An example of polyethylene glycol polymers includes but is not limitedto Carbowax Sentry 1000.

The structural agents are incorporated in the final formulation at alevel of about 5-50% by weight.

As for gelling agents which are also used in an amount of 5-50% byweight of the final formulation, subgeneric classes include but are notlimited to silicone elastomers, gelled natural and mineral oil systemsand gelled mineral oil and polymer systems.

Preferred examples of silicone elastomers include but are not limited tocyclomethicone and dimethicone cross polymers e.g. Dow Corning 9040,polysilicone-11 mixtures, e.g. Gransil PM Gel, and Gransil DCM, andGransil DMIG-6.

Preferred examples of gelled natural and mineral oil systems include butare not limited to a mixture of canola oil and silica and corn starch,e.g. Vegelatum Clear; a mixture of canola oil, soy bean germ extract,corn starch and silica, e.g. Vegelatum Equiline; gelled castor oil andrice bran oil (Natunola Health).

Preferred examples of gelled mineral oil and polymer systems include butare not limited to esters of hydrogenated polyisobutene,ethylene/propylene/styrene copolymers, and butylene/ethylene/styrenecopolymers, e.g. Versagel M, ME, MC, MD, ME, MJ and MP (Penreco Corp.);and polybutene, e.g. Indopol H-100.

The total amount of the sum of the structural agent and gelling agentwill be determined by the desired rheological properties of the finalformulation. As a guideline, the total amount of the sum in the finalformulations will be in the range 5-90% by weight.

The substantially anhydrous delivery system of the present invention canbe utilized for the incorporation of any PE-extract; however, thedelivery system is particularly beneficial for the incorporation of thestandardized extract described above and especially the commercialproduct EMBLICA™. It is also contemplated that the anhydrous deliverysystem of the present invention can be utilized for the incorporation ofother active materials.

Additional ingredients can be added to the formulation for their knownfunctions, for example skin lightening agents, skin brightening agents,skin even-toning agents, anti-aging agents, sunscreen agents, andantiperspirant/deodorant agents, herbal products, vitamins, andmedicaments. Since rheological properties of the final product willprimarily be dependent on the nature and proportion of the vehicle andthe structural and gelling agents of same, the formulator can tailormake the final formulation to the desired product, e.g. semi-solid orgel.

Examples of antiperspirant agents include but are not limited toaluminum zirconium tetrachlorohydrex GLY (coordination complex ofaluminium zirconium tetrachlorohydrate and glycerine)

Examples of additives for skin feel and adhesion include but are notlimited to bismuth oxychloride, Boron Nitride, PPG-3 myristyl ether,glyceryl laurate, PEG-40 castor oil and PEG-derivatives of fattyalcohols and mixtures thereof. With respect to bismuth oxychloride inparticular, it has been discovered that by the addition of same,important advantageous properties are imparted to the composition. Thus,the appearance and consistency of the final product may be improvedconsiderably by the addition of generally about 0.5 to 20%, preferably 2to 10% by weight, of powdered bismuth oxychloride pigment (e.g., BironoLF-2000). The formulated product with the pigment is whiter, has a moresubstantial appearance, and offers a much drier, silkier skin feel, thanthe same product without this pigment. Adhesion to the skin is alsoimproved with the addition of this pigment. A list of some presentlycommercially available bismuth oxychlorides is given below. CommercialParticle Size in μm Bismuth Distinguishing (Laserbeam Diffraction;Oxychloride Feature Malvern 2000) Biron ® B50 Moderately heavy  2.0-35.0(80% within range) powder  9.0-15.0 (D50: median size) Biron ® FinesSlightly less heavy,  2.0-35.0 (80% within range) fine powder  9.0-15.0(D50: median size) Mibiron ® 50% mica <50 (80% within range) N5016.0-22.0 (D50: median range) Biron ® NLD Surfactant-treated,  2.0-25.0(80% within range) improved dispersibility  6.0-12.0 (D50: median range)Biron ® ESQ Matte, less hiding,  2.0-35.0 (80% within range) excellentskin adhesion 11.0-17.0 (D50: median range) Biron ® Light-stable,excellent <35.0 (80% within range) LF-2000 skin-feel 8.0-20.0 (D50:median size) Biron ® Dispersed in BiOCl (68.0-72.0%) Liquid SilverOctylhydroxy stearate, Ethyhexyl Hydroxystearate Highly lustrous(28.0-32.0%) Biron ® MTU Matte, transparent &  2.0-35.0 (80% withinrange) light-stable 12.0-18.0 (D50: median size)

Iridescent bismuth oxychloride coated mica pigments are alsocontemplated. Whereas all bismuth oxychloride pigments will provideadvantageous properties, the preferred pigments are Biron® LF-2000 andBiron® MTU.

Biron® LF-2000 is a white pigment having particle size (determined byLaserbeam Diffraction; Malvern 2000)<35 μm (80% within range) and8.0-20.0 μm (D50: median size) which offers excellent skin feel, andadds some luster to the final product, and Biron® MTU is a white pigmenthaving particle size 2.0-35.0 μm (80% within range) and 12.0-18.0 μm(D50: median range) which also offers improved skin feel and a morematte look to the product on the skin.

Other sources of Bismuth oxychloride can also be included in theinvention, such as, a range of Bismuth oxychloride products availablefrom Engelhard. These are: Pearlite ® 01 UVS Some light-stability,lustrous Pearlite ® 02 UVS Some light-stability, matte Pearlite ® 03Lustrous, poor UV stability Pearlite ® 04 Matte, poor UV stabilityMearlite ® GBU Matte, poor UV stability Mearlite ® LBU Lustrous, poor UVstability Mearlite ® GLS Some light-stability, lustrous Pearl-Glo ® UVRSome light-stability, lustrous

The advantages of the addition of bismuth oxychloride will benefit otheranhydrous compositions having different or no anti-oxidants, i.e.compositions without PE. Such other compositions include color cosmeticproducts such as lipsticks, lip glosses, and lip balms. Anhydrouscream-to-powder foundations, creamy eye shadow, and blushers may alsobenefit from such a delivery system. Hair pomades, shaping balms, andmolding waxes may also be formulated with this delivery system, as canvarious anhydrous ointment systems for such applications as diaper rash,muscle aches, and burns. It is also to be understood that PE, because ofits antioxidant, anti-aging, skin lightening and skin even toningproperties will impart improved properties to all of the products.

Other antioxidants may be incorporated in the system which includemixtures of antioxidants suitable for use in the cosmetic formulations.Known and commercial mixtures are, for example, mixtures comprising, asactive ingredients, lecithin, L-(+)-ascorbyl palminate and citric acid(e.g. Oxynex® AP), natural tocopherols, L-(+)-ascorbyl palmitate,L-(+)-ascorbic acid and citric acid (e.g. Oxynex® K LIQUID), tocopherolextracts from natural sources, L-(+)-ascorbyl palmitate, L-(+)-ascorbicacid and citric acid (e.g. Oxynex® L LIQUID), DL-α-tocopherol,L-(+)-ascorbyl palmitate, citric acid and lecithin (e.g. Oxynex® LM) orbutylhydroxytoluene (BHT), L-(+)-ascorbyl palmitate and citric acid(erg. Oxynex® 2004).

The formulations according to the invention can comprise vitamins asfurther ingredients. Preferably, vitamins and vitamin derivatives chosenfrom vitamin A, vitamin A propionate, vitamin A palmitate, vitamin Aacetate, retinol, vitamin B, thiamine chloride hydrochloride (vitaminB1), riboflavin (vitamin B2) nicotinamide, vitamin C (ascorbic acid),vitamin D, ergocalciferol (vitamin D2), vitamin E, DL-tocopherol,tocopherol E acetage, tocopherol hydrogen-succinate, vitamin K1, esculin(vitamin P active ingredient), thiamine (vitamin B1) nicotinic acid(niacin), pyridoxine, pyridoxal, pyridoaxmine, (vitamin B6),panthothenic acid, biotin, folic acid and cobalamine (vitamin B12) arepresent in the cosmetic formulations according to the invention,particularly preferably vitamin A palmitate, vitamin C, DL-tocopherol,tocopherol E acetate, nicotinic acid, panthothenic acid and biotin.

Compositions of the present invention may also comprise one or moreorganic sunscreens. Suitable sunscreens can have UVA absorbingproperties, UVB absorbing properties or a mixture thereof. The exactamount of the sunscreen active will vary depending upon the desired sunprotection factor, i.e. the “SPF” of the composition as well as thedesired level of UVA protection. The compositions of the presentinvention preferably comprise an SPF of at least 10, preferably at least15. (SPF is a commonly used measure of photoprotection of a sunscreenagainst erythema. The SPF is defined as a ratio of the ultravioletenergy required to produce minimal erythema on protected skin to thatrequired to products the same minimal erythema on unprotected skin inthe same individual. See Federal Register, 43, No 166, pp. 38206-38269,Aug. 25, 1978). Compositions of the present invention preferablycomprise from about 2% to about 25%, more typically from about 4% toabout 15%, by weight, of organic sunscreen. Suitable sunscreens include,but are not limited to, those found in the CTFA International CosmeticIngredient Dictionary and H handbook, 7.sup.th edition, volume 2 pp.1672, edited by Wenninger and McEwen (The Cosmetic, Toiletry, andFragrance Association, Inc., Washington, D.C., 1997).

The compositions of the present invention preferably comprise a UVAabsorbing sunscreen actives that absorb UV radiation having a wavelengthof from about 320 nm to about 400 nm. Suitable UVA absorbing sunscreenactives are selected from dibenzoylmethane derivatives, anthranilatederivatives such as methylanthranilate and homomethyl,1-N-acetylanthranilate, and mixtures thereof. Examples ofdibenzoylmethane sunscreen actives are described in U.S. Pat. No.4,387,089; and in Sunscreens: Development, Evaluation, and RegulatoryAspects, Second edition, edited by N. J. Lowe and N. A. Shaath, MarcelDekker, Inc. (199,). The UVA absorbing sunscreen active is preferablypresent in an amount to provide broad-spectrum UVA protection eitherindependently, or in combination with, other UV protective actives thatmay be present in the composition.

Preferred UVA sunscreen actives are dibenzoylmethane sunscreen activesand their derivatives. They include, but are not limited to, thoseselected from 2-methyldibenzoylmethane, 4-methyldibenzoylmethane,4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane,2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane,4,4′-diisopropylbenzoylmethane, 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane,2-methyl-5-isopropyl-4′-methoxydibenzoylmethane,2-methyl-5-tert-butyl-4′-methoxy-dibenzoylmethane,2,4-dimethyl-4′-methoxydibenzoylmethane,2,6-dimethyl-4′-tert-butyl-4′methoxydibenzoylmethane, and mixturesthereof. Preferred dibenzoyl sunscreen actives include those selectedfrom 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane,4-isopropyldibenzoylmethane, and mixtures thereof.

A more preferred sunscreen active is4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane also known as butylmethoxydibenzoylmethane or Avobenzone.

The compositions of the present invention preferably further comprise aUVB sunscreen active that absorbs UV radiation having a wavelength offrom about 290 nm to about 320 nm. The compositions preferably comprisean amount of the UVB sunscreen active that is safe and effective toprovide UVB protection either independently, or in combination with,other UV protective actives that may be present in the compositions. Thecompositions preferably comprise from about 1% to about 15%, morepreferably from about 1% to about 12%, of UVB absorbing organicsunscreen.

A wide variety of UVB sunscreen actives are suitable for use herein. Alist of currently approved sunscreens can be found in Organic Sunscreenspublished by R. Chaudhuri et al. in The Chemistry and Manufacture ofCosmetics, Vol. III, pages 627-644 (2002). Preferred UVB sunscreenactives are 3 selected from 2-ethylhexyl-2-cyano-3, 3-diphenylacrylate(referred to as octocrylene), Homomenthyl salicylate,2-phenyl-benzimidazole-5-sulphonic acid (PBSA), cinnamates and theirderivatives such as 2-ethylhexyl-p-methoxycinnamate andoctyl-p-methoxycinnamate, TEA salicylate, octyldimethyl PABA, camphorderivatives and their derivatives, and mixtures thereof. Salt and acidneutralized forms of the acidic sunscreens are also useful herein. Whenorganic sunscreen salts, such as PBSA, are used within compositions ofthe present invention they can disrupt the action of the thickener withthe result that the final product may have sub optimal rheology. Thiscan be countered by the addition of higher levels of thickener, fattyalcohols or nonionic surfactants such that the rheology of the finalproduct returns to the desired level.

An agent may also be added to any of the compositions useful in thepresent invention to stabilize the UVA sunscreen to prevent it fromphoto-degrading on exposure to UV radiation and thereby maintaining itsUVA protection efficacy. Wide ranges of compounds have been cited asproviding these stabilizing properties and should be chosen tocompliment both the UVA sunscreen and the composition as a whole.Suitable stabilizing agents include, but are not limited to, thosedescribed in U.S. Pat. Nos. 5,972,316; 5,968,485; 5,935,556; 5,827,508and Patent WO 00/06110. Preferred examples of stabilizing agents for usein the present invention include2-ethylhexyl-2-cyano-3,3-diphenylacrylate (referred to as octocrylene),ethyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl-3,3-diphenylacrylate,ethyl-3,3-bis(4-methoxyphenyl)acrylate, and mixtures thereof.Di-2′-ethylhexyl-3,5-dimethoxy-4-hydroxy benzylidene malonate and otherderivatives as exemplified in U.S. Ser. No. 09/904,904 filed Jul. 16,2001 and Ser. No. 10/022, 343 filed Dec. 20, 2001, and publishedInternational Application No. PCT/EP 02/06743.

To summarize the quantitative amounts described above, the finalformulation on a weight basis comprises in general about 20-80%,preferably 20-60% of a substantially anhydroLs liquid vehicie, a totalof about 5 to about 90% of a structural and/or gelling agent, and0.05-10%, preferably 0.1-3% of a PE extract, especially the extracthaving the trademark EMBLICA. Other components, especially bismuthoxychloride, can be incorporated in percentages that function for theirintended purpose. The preferred combination of ingredients is 30-40%silicone oils (such as, 36.6% cyclomethicone), 50-70% structural orgelling agents (such as, 9.0% beeswax, 5.0% ozokerite, 45.4% Dow Corning9040 Silicone Elastomer, 3.0%), 1-5% Bismuth oxychloride (such as, 3.0%Biron® LF-2000), and 0.1 to 5.0% PE extract (such as, 1.0% Emblica).

In order to produce the desired delivery system and the finalformulation, there are several alternative processes which can beutilized. For example it is contemplated that all the desired componentscan be blended together under sufficient heat and mixing in a singlestep in order to form the final formulation. An improved process,however, involves more than one step.

Based on 100 parts by weight of the final formulation, the first stepcomprises blending a mixture of about 5 to 80% of a vehicle and 5 to 90of a structural or gelling agent with sufficient heat, e.g. atemperature of about 60 to 90° C. and mixing until a clear and uniformmixture is obtained.

In a separate step the PE extract is mixed with a minor amount of, e.g.1 to 20% of the same vehicle used in the first step together with aminor amount 1 to 30% of a structural and/or gelling agent. Thissubsequent step is important insofar as the mixture should be blendedwith sufficient heat but preferably below 60° C. until it is relativelysmooth and contains no visible lumps. The product from this subsequentstep is then mixed with that of the first step containing the majoramounts of vehicle and structural/gelling agents, the mixing beingconducted at preferably below 60° C., for example 40-50° C. so as toavoid any decomposition of the PE extract. By virtue of this two stepoperation, the ingredients in the first step can be heated to a highertemperature which will facilitate mixing, and the resultant mixture thencan be cooled to below 60° C. before mixing with the minor compositioncontaining the PE extract and the minor amounts of vehicle andstructural/gelling agents.

Optionally, other components can be added: for example after the firststep, an antiperspirant agent can be added to the product of the firststep and then blended therein. In such a process, the subsequent stepmentioned above, would be a third step after the antiperspirant agent isblended and the resultant mixture is cooled to below 60° C.

Final product can be packaged in any suitable container for daily usefor multiple applications. Also, this product can be provided as asingle dose application, for example in gelatin capsules.

Without further elaboration, it is believed that one skilled in the artcan, using the preceding description, utilize the present invention toits fullest extent. The following preferred specific embodiments are,therefore, to be construed as merely illustrative, and not limitative ofthe remainder of the disclosure in any way whatsoever.

In the foregoing and in the following examples, all temperatures are setforth uncorrected in degrees Celsius; and, unless otherwise indicated,all parts and percentages are by weight.

EXAMPLE 1 Anhydrous Delivery System for Emblica™ without bismuthOxychloride

INCI NAME TRADE NAME/MANUFACTURER % Phase A Beeswax White BeeswaxSP-422/Strahl & 9.00 Pitsch Ozokerite White Ozokerite SP-1020/Strahl &5.00 Pitsch Cyclomethicone Dow Corning 345 Fluid/Dow Corning 36.00Cyclomethicone (and) Down Corning 9040 Silicone 40.00 DimethiconeElastomer Blend/Dow Corning Crosspolymer Phase B Cyclomethicone DowCorning 345 Fluid/Dow Corning 3.60 Cyclomethicone (and) Dow Corning 9040Silicone Elastomer 5.40 Dimethicone Blend/Dow Corning CrosspolymerPhyllanthus emblica Emblica ™/RONA 1.00 fruit extract Total 100.00Procedure: Blend ingredients in Phase A; heat with mixing at about70<80° C. until clear and uniform. Blend ingredients in Phase Bseparately at a temperature below 60° C., e.g. room temperature; themixture should be smooth and contain no lumps. Cool Phase A to about 60°C. and add Phase B with mixing. When the mixture is uniform it may bepackaged.

EXAMPLE 1A With Bismuth Oxychloride

INCI NAME TRADE NAME/MANUFACTURER % Phase A Beeswax White BeeswaxSP-422/Strahl & 9.00 Pitsch Ozokerite White Ozokerite SP-1020/Strahl &5.00 Pitsch Cyclomethicone Dow Corning 345 Fluid/Dow Corning 36.00Cyclomethicone (and) Down Corning 9040 Silicone 40.00 DimethiconeElastomer Blend/Dow Corning Crosspolymer Phase B Bismuth OxychlorideBiron ® LF-2000/Rona 3.00 Phase C Cyclomethicone Dow Corning 345Fluid/Dow Corning 3.60 Cyclomethicone (and) Dow Corning 9040 SiliconeElastomer 5.40 Dimethicone Blend/Dow Corning Crosspolymer Phyllanthusemblica Emblica ™/RONA 1.00 fruit extract Total 100.00Procedure: Blend ingredients in Phase A; heat with mixing until clearand uniform. Blend bismuth oxychloride into Phase A. Blend ingredientsin Phase C separately; the mixture should be smooth and contain nolumps. Cool Phase A to 60-65° C. and add Phase C with mixing. When themixture is uniform it may be packaged.

The addition of bismuth oxychloride as the lustrous white powder Biron®LF-2000 whitens the gel and allows for greater skin adhesion and a muchsmoother, silkier skin feel to the final product. These benefits canalso be obtained in other systems, as illustrated in Examples 3 and 4below. Note that the viscosity of the final product may be varied, froma stable solid, as in Examples 1, 2 and 3, to a flowable gel, as inExample 4. In these formulas, as above, Biron® LF-2000 adds whiteness, asmoother skin feel, and greater skin adhesion to the final product.

EXAMPLE 2 Antiperspirant with Emblica™

INCI NAME TRADE NAME/MANUFACTURER % Phase A Stearyl Alcohol CrodacolS-70/Croda 18.00 Hydrogenated Castor Wax/Ross 5.00 Castor OilCyclomethicone Dow Corning 345 Fluid/Dow Corning 40.90 PPG-3 MyristylEther Varonic APM/Goldschmidt 3.00 Glyceryl Laurate Jeechem MLD/Jeen4.00 Phase B Aluminum Zirconium Rezal 36 GP Superfine/Reheis 20.00Tetrachlorohydrex GLY Bismuth Oxychloride Biron © MTU/RONA 4.00 Phase CCyclomethicone Dow Corning 345 Fluid/Dow Corning 1.80 Cyclomethicone(and) Dow Corning 9040 Silicone 2.70 Dimethicone Elastomer Blend/DowCorning Crosspolymer Phyllanthus emblica Emblica ™/RONA 0.50 FruitExtract Phase D Fragrance Grapefruit Fragrance 26520M/Shaw 0.10 MudgeTotal 100.00Procedure: Blend ingredients in Phase A; heat with mixing at 70-80° C.until clear. Add Phase B with mixing. Blend ingredients in Phase Cseparately; the mixture should be smooth and contain no lumps. Cool thePhase A/B mixture to below 60° C., e.g. 40-50° C. and add Phase C withmixing. Add Phase D with mixing. Package.

EXAMPLE 3 Anhydrous Oil-Free Emblica™ Gel

INCI NAME TRADE NAME/MANUFACTURER % Phase A Ozokerite White OzokeriteSP-1020/Strahl & 3.00 Pitsch Cyclomethicone Dow Corning 345 Fluid/DowCorning 25.00 Cyclomethicone (and) Gransil GCM/Grant Industries 60.00Polysilicone-11 Phase B Bismuth Oxychloride Biron ® LF-2000/Rona 2.00Phase C Cyclomethicone Dow Corning 345 Fluid/Dow Corning 3.60Cyclomethicone (and) Dow Corning 9040 Silicone Elastomer 5.40Dimethicone Blend/Dow Corning Crosspolymer Phyllanthus emblicaEmblica ™/RONA 1.00 Fruit Extract Total 100.00Procedure: Blend ingredients in Phase A; heat with mixing until clearand uniform. Add bismuth oxychoride and disperse with mixing. Blendingredients in Phase C separately; the mixture should be smooth andcontain no lumps. Cool Phase A/B to 50-60° C. and add Phase C withmixing. When the mixture is uniform it may be packaged.

EXAMPLES 4-9 Additional Formulas with Phyllanthus emblica Extract

Formula Number Raw Material 4 5 6 7 8 9 PHASE A Ozokerite 2.80 5.00 6.005.00 3.00 3.00 Dow Corning 345 48.50 30.00 50.00 25.00 27.00 25.00Dimethicone (and) 38.70 — — 60.00 60.00 — Polysilicone-11 (1) PhenylTrimethicone (and) — 55.00 — — — — Polysilicone-11 (2) Cyclomethicone(and) — — 34.00 — — — Dimethicone Crosspolymer (3) Cyclomethicone (and)— — — — 60.00 Polysilicone-11 (4) Bismuth Oxychloride (5) — — — — — 2.00PHASE B Dow Corning 345 3.60 3.60 3.60 3.60 3.60 3.60 Cyclomethicone(and) 5.40 5.40 5.40 5.40 5.40 5.40 Dimethicone Crosspolymer (3)Phyllanthus emblicaextract 1.00 1.00 1.00 1.00 1.00 1.00 Total 100.00100.00 100.00 100.00 100.00 100.00Procedure: Follow procedure as described in the Example 3Note:Trade Names(1) Gransil DMG-6, Grant Industries(2) Gransil PM Gel, Grant Industries(3) Dow Corning 9040 Silicone Elastomer Blend, Dow Corning(4) Gransil GCM, Grant Industries(5) Biron LF-200, Rona

The preceding examples can be repeated with similar success bysubstituting the generically or specifically described reactants and/oroperating conditions of this invention for those used in the precedingexamples.

EXAMPLE 10 Anhydrous System with Sunscreens

INCI NAME TRADE NAME/MANUFACTURER % Phase A Beeswax White BeeswaxSp-422/Strahl & 9.00 Pitsch Ozokerite White Ozokerite SP-1020/Strahl &5.00 Pitsch Cyclomethicone Dow Corning 345 Fluid/Dow 36.00 CorningCyclomethicone (and) Dow Corning 9040 Silicone 37.00 DimethiconeElastomer Blend/Dow Corning Crosspolymer Phase B Bismuth OxychlorideBiron ® LF-2000/Rona 3.00 Phase C Ethylhexylmethoxy Eusolex 2291/Rona6.00 cinnamate Avobenzone Eusolex 9020/Rona 2.00 Di-ethylhexyl- OxynexST/Rona 2.00 Syringylidene malonate Total 100.00

Procedure: Blend ingredients in Phase A; heat with mixing until clearand uniform. Blend bismuth oxychloride into Phase A. Blend ingredientsin Phase C separately; apply heat if needed. Cool Phase A to 60-65° C.and add Phase C with mixing. When the mixture is uniform it may bepackaged.

EXAMPLE 11 Anhydrous System with Sunscreens

INCI NAME TRADE NAME/MANUFACTURER % Phase A Beeswax White BeeswaxSp-422/Strahl & 9.00 Pitsch Ozokerite White Ozokerite SP-1020/Strahl &5.00 Pitsch Cyclomethicone Dow Corning 345 Fluid/Dow Corning 36.00Cyclomethicone (and) Dow Corning 9040 Silicone 37.00 DimethiconeElastomer Blend/Dow Corning Crosspolymer Phase B Bismuth OxychlorideBiron ® LF-2000/Rona 3.00 Phase C Homosalate Eusolex HMS/Rona 6.00Avobenzone Eusolex 9020/Rona 2.00 Di-ethylhexyl-Syringal Oxynex ST/Rona2.00 malonate (proposed) Total 100.00

Procedure: Blend ingredients in Phase A; heat with mixing until clearand uniform. Blend bismuth oxychloride into Phase A. Blend ingredientsin Phase C separately; apply heat if needed. Cool Phase A to 60-65° C.and add Phase C with mixing. When the mixture is uniform it may bepackaged.

The entire disclosure of all applications, patents and publications,cited above and below, including but not limited to U.S. patentapplication Ser. No. 10/120,156 filed Apr. 11, 2002 and Provisionalapplication 60/395,612 filed Jul. 5, 2002 is hereby incorporated byreference.

From the foregoing description, one skilled in the art can easilyascertain the essential characteristics of this invention and, withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various usages andconditions.

1. An anhydrous composition comprising (a) an antioxidant comprisingover 40% by weight of hydrolysable tannins having a molecular-weight ofless than 1,000. (b) a substantially anhydrous or non-aqueous liquidvehicle functioning to disperse the antioxidant.
 2. An anhydrouscomposition according to claim 1, wherein the antioxidant comprisesEmblicanin A, Emblicanin B, Pedunculagin and Punigluconin, preferably inan amount of 40-80% by weight.
 3. An anhydrous composition according toclaim 1, wherein the antioxidant comprises by weight: 20-35% EmblicaninA, 10-20% Emblicanin B, 15-30% Pedunculagin-and 3-12% Punigluconin andpreferably the antioxidant has a content of Rutin of less than 0.01% byweight and preferably of flavonoids in general of less than 0.01% byweight.
 4. A composition according to claim 1, wherein the antioxidanthas maximum absorbances (optical density) in the UV region of 0.8 atwavelength 410 nm, 0.1 at wavelength 470 nm, 0.08 at wavelength 530 nm,0.09 at wavelength 590 nm, and 0.02 at wavelength 650 nm.
 5. Ananhydrous composition according to claim 1, wherein the substantiallyanhydrous or non-aqueous liquid comprises at least one member selectedfrom the group consisting of silicone fluids, organic esters andglycols, wherein the composition comprises preferably at least onesilicone fluid.
 6. An anhydrous composition according to claim 1,wherein the composition further comprises at least one structural agentand wherein said structural agent is preferably selected from the groupconsisting of high melting point fatty alcohols, glycerol esters, glycolesters, polyethylene polymers and polyethylene glycol polymers.
 7. Ananhydrous composition according to claim 1, wherein the compositionfurther comprises a gelling agent, wherein said gelling agent preferablycomprises at least one member selected from the group consisting ofsilicone elastomers, gelled natural and mineral oil systems, and gelledmineral oil and polymer systems.
 8. An anhydrous composition accordingto claim 1, wherein the composition further comprises at least onesunscreen.
 9. An anhydrous composition according to claim 1, furthercomprising an amount of bismuth oxychloride sufficient to impart animproved skin feel to the composition, wherein the bismuth oxychlorideis preferably included as a predispersion.
 10. A method of producing ananhydrous composition according to claim 1, said anhydrous compositionfurther comprising each one of a structural and gelling agent, saidprocess comprising the steps of: (1) mixing up to 80% of saidsubstantially anhydrous or non-aqueous vehicle and 5 to 90% of astructural and/or gelling agent with sufficient heat and mixing until aclear and uniform mixture is obtained. (2) mixing the anti-oxidant witha minor amount of about 1-20% of said substantially anhydrous ornon-aqueous vehicle with a minor amount of about 1-30% of saidstructural and/or gelling agent, under a sufficient heat but below 60°C. until it contains no visible lumps, and (3) mixing the product ofstep (2) with the product of step (1) at below 50° C.